Bis-sulfonyltriazenes



United States Patent BIS-SULFON-YLTRIAZENES William Baptist Hardy andFrederic Henry Adams, BoundBrook, N. J., assi'gnors to American CyanamidCompany, New York, N. Y., a corporation of.Maine N0. Drawing.Application. December 14, 1954,

Serial No..475,-,285

6 Claims. (Cl; 260-140) This-inventionrelates to a new class ofcompounds. More particularly, it relates to bis-sulfonyltriazenes of theformula The new compounds, in accordance with this invention,, areuseful in the fields of pharmaceuticals, dyes, rubber processing and thelike. Specifically, it has been found that these compounds areparticularly useful as'blowing agents in the preparation of cellularrubber and plastic materials.

In preparation of the new sulfonyltriazenes, a tetrazonium salt can bereacted with a stoichiometrically equiva- Ice 2. 4,4-diamino-diphenyl,.4;4'-diamino-diphenyl' ether, 4;-4 diamino-dip-henyl sulfide,4,4'-diamino-3,3-dimethoxy-diphenyl, 4,4'-diamino-3,3-dimethyl-diphenyl,4,4' -diamino- 1,1'-dinaphthyl and the like.

The monosulfonamide with which'th'e tetrazo compound is coupled to formthe intermediate tetrazo sulfonamide may be widely varied. Examples ofsuch sulfonamides include, for instance, cycloalkylsulfonanrides,suchwas cyclohexane sultonamide; aralkylsulfonami des such as phenylmeth anesulfonarnide, phenylethanesulfionamide, and 2-, 3- and4-nitrop-henylmethanesulfionamides; arylsulfonam'idessuch.as'benzenesulfonamide, o-, mand pethylbenzenesulfonamide, o-, m andp-chlorobenzenesulfonamides, 0-, mandp-rnethoxybenzenesulfonamides,.or,mand p-methylbenzenesulfonamides, o-xyl'ene-Z, 3-, 4- and 5-,sulfonamides, biphenyl-4-sulfonamide, 1- and 2- naphthalenesulfonamides;1:-nitro- 3-, 4-, 5-, 6-, 7-, and S-naphthalene sulfonamides,1-acetoxynaphthalene-o-sulfonam'ide, 2-chloronaphthalene-G-sulfonamide;anthracene-land2-sulfonamides, phenantlirene-2,3- and 9- sulfon-amides,and acenaphthene-3-sulfonamide; and heterocyclic sulfonamides such as3=py-ridine-sulfonarnide, quinlent amount of a selected sulfonamide toform the interme- I oline-S-sulfonamide, isoqu'inoline 5- andS-sulfionamide, benzimidazole-S-sulfonamide, 2acetoxycarbazole-7-sulfonamide, 1,2-benzocarbazole-3-sulfonamide,dibenzofuran-Z-sulfonamide, 2 acetamidothiazole-S-sulfo-namide, and thelike.

The intermediate tetrazoamide compounds soo'btained are then treated'toobtain N-substituted sulfonyltriazenes of this invention. The R2 residueso obtained is an aliphatic radical linked through a saturated carbonatom to the nitrogen. As examples, there might be mentioned lower alkylradicals such as methyl, ethyl, propyl, butyl and thelikeandc'hl-oro-derivatives thereof; alkenyl radicals such as allyl;acrylonitrile, methacryl-onitrile, crotononitrile,fl-ethylacrylonit-rile, B-isopropylacrylonitrile,p-isobutylacrylonitrile and-the like; aralkyl radicalssuch as benzyl andp'henylethyl and the like.

The invention is further illustrated by the following examples which arenot intended to be limiting. Unless otherwise noted, allparts are byweight;

EXAMPLE 1v triazene'] (in, 0H,

diate tetrazosulfonami-de. The intermediate can then be aikylated usinga lower dialkyl sulfate such as dimethylor" diethylsulfate. TheN-s'ubstitution may also be accomplished in a manner other: than bydirect alkylation. Where, for instance, the substituent is to be acyanoalkyl, the tetrazosulfonamide may be reacted with an acrylonitrile.This latter procedure forms the subject matter of copending applicationfor U. S. Letters Patent, Serial No. 475,283, of the applicants herein,filed of even date.

The tetrazo compounds employed in the preparation of;

the intermediate product are preferably salts of 4,4-diamino-diarylenein which the nuclei of the diarylene radical may or may not beinterposed by an oxygen or sulfur atom. For example, the-re may beemployed salts of EXAMPLE 2 3,3 [4,4'-(3,3 dimethyl-biphenyll-bis-"(i-methyl-l-benzenesulfonyltriazene) 3 4 To 125 parts of watermixed with 107 parts of 37.5% EXAMPLE 5 hydrochloric acid is added 31.8parts of 4,4-diamino-3,3- A rubber stock containing the po of Q PPdimethyl-biphenyl. After cooling with ice, to about 5 C., 1 was preparedaccording to the following compositlon: 60 parts by volume of 5 N sodiumnitrite solution is 5 fi f Parts asticized rubber 100 added. Aftertetrazotizatron is complete ,the tetrazo Stearic acid 2 solution isclarified by filtration with animal charcoal and Zi id 5 added to a coldsolution of 48 parts of benzenesulfon- Keystone Whiting 50 amide in amixture of 2000 parts of water and 122 parts gP ight process aid 10 of50% sodium hydroxide solution. The solution is kept Petrolatum 3 cold byaddition of ice as necessary. After the reaction methylene bis 4 methyl6 with the tetrazo compound is complete, 80 parts of dibutyl phenol) 0.5methyl sulfate is gradually added. The product which 15 h 1 di md 36separates, 3,3'-[4,4-(3,3'-dimethyl-biphenyl)] -bis-(3- i' jg i fi g g emethyl-l benzenesulfonyltriazene), is isolated by filtra- (4,4, iYTL;Tgfggiti: tion, washed with water and dried sulfonyl triazene 1.5

EXAMPLE 3 1 ,3' dimethoxy biphenyh] bis (3 methyl 1benzenesulfonyl-triazene C H; CH CH CH;

The procedure of Example 2 is repeated except that Samples of the stockwere blown at 153 C. for 36.6 parts of4,4-diarnino-3,3-dimethoxybiphenyl is used minutes and 130 C. for 60minutes. The mold size in place of 31.8 parts of4,4-diamino-3,3-dimethylbiwas 6 cubic inches and both high and low loadswere 'phenyl. blown. In the case of white stock, the respective portionsEXAMPLE 4 3,3 [4,4' (1,1' binaphthyl)] bis (3 methyl-1-benzenesulfonyltriazene) To solution of 107 parts of 37% hydrochloricacid in for high and low loads are 51 grams and 42 grams. For

125 R of is added, with stirring; Pafts of neutral colored stock theyare 48.5 grams and grams. 4,4'-d1ammo-1,1-b1naphthyl. After cooling withice to C. pa 11s by Volume of 5 N sodium nitrite Solution In eachinstance, a completely blown, substantially coloris added. The mixtureis stirred until tetrazotization is less Prodct of uniform fine canstructure was Obtamedcomplete, the solution filtered and added to a coldsolu- 50 W claim;

tion of 48 parts of benzenesulfonamide in a mixture of 1,Bis-sulfontriazgnes f h f l 2000 parts or water and 122 parts of 50%sodium hydroxide solution. The solution is kept at a low temperature byoccasional addition of ice. 80 parts of dimethyl sull R- fate isgradually added and stirring continued until the sot-N N N reaction issubstantially complete. The product which RX separates, 3,3 (4,4 1,1binaphthyl) bis (3- RSO:N=N-N/ methyl 1 benzenesulfonyltriazine), isisolated by filtra- 2 tion, washed with water and dried.

EXAMPLE 5 3,3 (4,4 diphenyl ether) bis (3 methyl 1benzenesulfonyltriazine) The procedure of Example 4 is repeated exceptthat 30 in which R is an aryl radical of the benzene and naphggrgsoft4,4f- :11Z i P 1 31Q gi l l gh tiy l 111 Place of thalene series; R1is selected from the group consisting .parso,-amno-,- To illustrate theuse of the new compounds of this of dlaryiene oxyblsflrylelle11017531716118 radlcals, invention as blowing agents in the formation ofcellular a R2 15 a lower ahphatlc al of l-4 carbon atoms products, thefollowing example was conducted. linked through a saturated carbon tothe nitrogen.

5 2. 3,3 (4,4' biphenyl) bis [3 methyl 1 benzenesulfonyl triazene] ofthe formula 3. 3,3 [4,4' (3,3 dimethyl diphenyn] bis (3- methyl 1benzenesulfonyltriazene) of the formula 4. 3,3 [4,4' (3,3 dimethoxybipheny1)] bis (3- methyl 1 benzenesulfonyltriazene) of the formula 5.3,3 [4,4' (1,1 binaphthyl)] bis (3 methyl- 1 benezenesulfonyltriazene)of the formula 6. 3,3 (4,4' diphenyl ether) bis (3 methyl 1-benzenesulfonyltriazene) of the farmula Q Q Q Q References Cited in thefile of this patent UNITED STATES PATENTS 2,117,251 Kleiderer et a1. May10, 1938 2,402,611 Dickey et a1. June 25, 1946

1. BIS-SULFONTRIAZENES OF THE FORMULA